Process for changing the tint of a photochromic material and material formed thereby

ABSTRACT

The tint of a photochromic material is changed without degradation in photochromic properties by heating the material in a reducing atmosphere and, while the photochromic material is at an elevated temperature, irradiating it with ultraviolet irradiation. While the heating in a reducing atmosphere itself causes a change in the tint of the photochromic material, the subsequent ultraviolet irradiation further emphasizes this change, generally yielding darker and deeper tints. The resulting material is also described.

United States Patent Simms [4 Nov. 18, 1975 3,449,103 6/1969 Stookey 65/30 OTHER PUBLICATIONS Photochromic Silicate Glasses Sensitized by Silver I-la- [761 lnventori Robe" A. Simms, 449 Ithaca Road, lides Science Apr. 10, 1964 vol. 144 pp. 150 154.

Horseheads, NY. 14845 [22] Filed: Feb, 1, 1974 Primary Examiner-Robert L. Lindsay, Jr.

Attorney, A ent, 0r Firm-Su hrue, Rothwell, Mion, 211 App]. No.: 438,835 Zinn & Maipeak g [52] US. Cl. 106/54; 65/30; 65/32; [57] ABSTRACT [51] Int Cl 2 65/DIG The tint of a photochromic material is changed with- [58] Field of Search 65/30, 33, 32, DIG. 2; 9" T photocllmmlc Pmpemes by 7 6 4 161/410 106/52 54 DIG 6 mg the material 1n a reducing atmosphere and, while I the photochromic material is at an elevated tempera- [56] R f (Tied ture, irradiating it with ultraviolet irradiation. While e erences l the heating in a reducing atmosphere itself causes a UNITED STATES PATENTS change in the tint of the photochromic material, the 2,649,387 8/1953 Parsons et al. 65/DIG. 2 subsequent ultraviolet irradiation further emphasizes 2,651,146 9/1953 Stookey 55/30 is change, generally yielding darker and deeper tints.

MOM-1118.11 et a]. X The resulting material is also described 3,325,299 6/1967 Arau o 65/30 X 3,420,698 l/l969 Smith 65/30 X 15 Claims, 1 Drawing Figure so A (UNTREATED) 1o 1 7 Y a'l TREATED) 60 A 1 so Mnm) U.S. Patent Nqv. 18, 1975 3,920,463

A (UNTREATED) B TREATED) A (n m PROCESS FOR CHANGING TI-IE TINT OF A PHOTOCI'IROMIC'MATERIAL AND MATERIAL FORMED THEREBY I BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to processes for changing the tint of a photochromic material and the material thus formed.

2. Description of the Prior Art Recently compositions have been developed which exhibit photochromic properties, i.e'., their optical transmittance varies reversibly with the intensity of actinic radiation incident. thereon.

Many photochromic compositions are substantially colorless or at best have a slight color when in the unexcited state. Coloring material is not often added to pho tochromic'compositions because of a decrease in the intensity of the photochromic change which may be caused thereby. There thus remains a substantial unmet demand for photochromic compositions of varying tints to meet various user requirements.

Although many photochromic materials are known, extensive development work has been done on the photochromic glasses. One of the original patents in this area is US. Pat. No. 3,208,860 Armistead et al. This patent describes inorganic silicate glasses containing sub-microscopic crystals of silver halides which darken in color when the glass is subjected to actinic radiation but which regain their original color when the actinic radiation is removed. The glasses described'in Armistead et al. are essentially colorless.

US. Pat. No. 3,449,103 Stookey is an improvement on the basic Armistead et 'al patent, and provides a process forincreasing the concentration of extremely finegr'ained silver halide crystals in the photochromic'glass of Armistead et al. by a rapid chillingof a melt of the photochromic glass during its formation.

US. Pat. No. 3,306,833 OLeary is a further improvement upon the disclosure of Armistead et al., suggesting that the p hototropic properties of the Armistead et al glas'ses can be improved by subjecting the glass bodies to exposure of X-rays or gamma-rays before or during the customary heat treating step in the formation of the glass. r 5 7 British Pat. Noel ,021 ,597 Coming Glass Works also relates to photochromic glasses "of the type described in Armistead et al., and suggests that such glasses can be improved by doping with cadmium oxide.

U.S. Pat. No. 3,615,771 Meiling discloses photochromic glasses within the CdO-B O -SiO field, describing the photochromic glasses as essentially free from fatigue.

US. Pat. No'. 3,617,316 Suzuki et'al. discloses photochromic glasses comprising a borate glass body containing microcrystals of a silver halide and copper oxide and a process for forming such glasses. The glasses are completely colorless or, at most, tinged with a very light yellow color. Copper oxide is a mandatory constituent which imparts photosensitivity to the photochromic glasses.

German Offenlegungschrift No. 2,107,343 discloses colored photochromic glasses comprising a silver hal-' ide containing borosilicate or borate glass containing minor proportions of vanadium, chromium,'manganese and/or cobalt in an electropositive valence state;

Russian Pat. No. 224,022 discloses that the photochromic characteristics of a photochromic glass can be improved by gamma irradiation prior to the customary heat treatment of the photochromic glass.

Belgian Pat. Abstract No. 692,626 discloses photochromic glasses which have a faintly yellowish color.

US. Pat. No. 3,269,847 and US. Pat. No. 3,278,319,

both in the name of Cohen, disclose photochromic glasses comprising, respectively, europium and cerium in the lower valency form. The glasses are formed in the presence of carbon (strong reducing conditions) in the melt stage. In the former patent, the higher the concentration of europium the more yellow is the unirradiated glass; this patent also discloses that the photochromic glass can be resensitized by high energy ultraviolet irradiation.

Ceramics, Vol. 68, 1968, page 10405, 1075 44m discloses the production of a photochromic glass and indicates, that by melting in a reducing atmosphere the pho-- tochromic properties of the glass disappear. This article also discloses that upon irradiation with ultraviolet radiation Ag and C1 are formed and darkening of the glasses occurs.

All of the above references disclose photochromic g'lass compositions amenable to processing in accordance with the present invention, and are hereby incorporated by reference in toto.

The majority of the above references do not deal with after-treatments for formed photochromic glasses, rather, they deal with the formation of bulk quantities of a photochromic glass. None of the above references suggest that the tint of a phtochromic article can be changed without substantial degradation of the photochromic properties thereof.

US. Pat. No. 3,464,806 Seki et al. discloses that metallized ceramic bodies can be obtained by causing metal oxides in a glass body to migrate from the glass body to the surface thereof during devitrification and then reducing the migrated metal oxide to the metal form on the glass body surface.

SUMMARY OF THE INVENTION It has now been discovered that the tint of a photochromic material can be permanently changed by heating the photochromic material in a reducing atmosphere and, while the photochromic material is at an elevated temperature, irradiating it with ultraviolet irradiation. While the heating in a reducing atmosphere itself causes a change in the tint of the photochromic 50 material, the subsequent ultraviolet irradiation further emphasizes this change, generally yielding darker and deeper tints. The resulting material is also described.

The first processing step effects a change in the tint of a photochromic material; the second process change accentuates the change in tint. The second processing step enables deeper tones to be achieved without degradation in photochromic properties than could be achieved by the use of the first processing step above.

Since many photochromic materials are substantially colorlessin the unexcited state, the process of the present invention can be used to'provide a permanent .tint to such material not only in the unexcited statebut in the excited state.

For those photochromic materials which are inherently colored, evenin the unexcited state, the process of the present invention can be applied to permanently change the tint of such materials, not only in the unexcited state but in the excited state.

It is thus one object of the present invention to provide photochromic materials ofvarying tints.

It is a further object of the present invention to provide photochromic articles of varying tints.

Still yet a further object of the present invention isto provide a process for changing the tint of a photochromic material or photochromic article without substantial changes in the photochromic properties of the material or article.

A specific object of the present invention is to provide photochromic glasses and photochromic glass articles of varying tints.

These and other objects of the present invention will be better understood from the following discussion.

BRIEF DESCRIPTION OF THE DRAWING The drawing is a plot of percent transmittance versus exposing wavelength for an untreated photochromic article and a photochromic article treated in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention finds application with photo'- chromic materials which undergo a transmissivity change upon exposure to visible light in general, including not only photochromic glasses but also photochromic plastic materials and the like.

The process of the present invention is applicable to photochromic materials in general due to the basic mechanism of the process of the present invention. More specifically,in almost all photochromic materials there is an excess of the active photochromic element present, e.g., in Armistead et al. glasses an excess of silver halide. While this excess does not harm the photochromic material, it provides no substantial increase in the photochromic effect. The reduction process of the present invention most preferably acts only on this excess active photochromic element since tinting is thus achieved without any substantial degradation in photochromic properties. However, it should be understood that this is not a mandatory bound on the present invention and, in fact, the reduction process of the present invention can be used to reduce active photochromic elements which is not considered excess as explained above. In this latter case, however, a slight decrease in photochromic properties will be exhibited. Many users will find the tinting effect of the process of the present invention to be so valuable, however, that they will accept not only a slight but a substantial decrease in photochromic properties to obtain a tinted photochromic material.

The present invention finds special application with photochromic glasses for two reasons: Firstly, photochromic glasses are today much more popular than photochromic plastics; secondly, photochromic glasses generally easily withstand the heating temperatures of the present invention, whereas special care must be taken in processing photochromic plastics so that they are not degraded at the heating temperatures of the present invention.

Preferred photochromic glasses are those disclosed in the Armistead et al. and Stookey patents heretofore cited, i.e., inorganic silicate glasses containing submicroscopic particles of silver halide.

Photochromic articles in any form can be processed in accordance with the present invention, for example, prescription and non-prescription eyeglasses which automatically become sunglasses when the wearer goes outside, specialized eyeglasses such as shooter's glasses, automobile windshields which darken and fade in response to sunlight, inlenses and filters required in optical instruments such as in cameras and the like, in building materials which regulate the amount of light which can enter a building, e.g., windows in homes, and the like.

One of the most important aspects of the present invention is that thetint of a photochromic article can be changed or darkened without any substantial harmful impact upon the photochromic properties of the article. Thus,'without any degradation in the photochromic properties one can obtain a wide spectrum of desired tints in accordance with the present invention, for example, inherently colorless photochromic materials can be tinted pink, yellow, light brown, dark brown, etc., and photochromic materials which are inherently colored can be changed to a deeper tint or tone or the color thereof changed, and little, if any, loss ofintensity or rapidity of the photochromic change is encountered.

The processing conditions of the present invention will now be discussed in detail:

1. heating a photochromic article in a reducing atmosphere;

2. irradiating the thus heated article with ultraviolet radiation while at an elevated temperature.

HEATING IN A REDUCING ATMOSPHERE The exact identity of the reducing atmosphere is not overly critical (so long as it is gaseous at the processing temperature, of course), and reducing atmospheres as are commonly used in the art can be used with success in the present invention. The reducing gas used must, of course, have a higher free energy of formation than that of visible light required to effect the transmissivity change in the photochromic material undergoing processing, e.g.,.greater than on the order of about 1% to about 2 electron volts.

On a commercial scale, cost and safety are the primary factors in selecting the reducing atmosphere, and preferred reducing gases comprise hydrogen, carbon monoxide, cracked ammonia and the like, which can be used in pure form or in an inert carrier gas.

Considering practical availability, usually hydrogen will be the reducing atmosphere used. While pure hydrogen can be used, in light of the danger of explosion and the relatively high cost thereof as compared to many inert carrier gases, generally the hydrogen will be used in combination with an inert gas carrier. Although one can, if desired, use exotic inert gases such as argon, neon and the like. for practical purposes the inert gas used will almost always be nitrogen, considering the cost and availability thereof. One should, of course, insure that oxygen is kept out of the system of the present invention to avoid the danger of explosion, even if an inert gas carrier is used.

There is no special criticality regarding the ratio of reducing gas to inert gas carrier (if such is used) from the viewpoint of the process mechanism. However, at extremely low proportions of reducing gas the process time is increased without attendant benefit in results, which is economically undesirable. Balancing all factors, a 5% hydrogen/% nitrogen (by volume) reducing atmosphere has been found to offer excellent results at reasonable processing times without undue costs or safety hazards, and such is most preferred for use in the process of the present invention.

Other reducing gas-inert carrier gas combinations are generally used in similar proportions. So long as the tinting effect of the present invention is achieved, little is gained by using greater amounts of reducing gas, though process time will be slightly decreased.

The process of the present invention can be practiced in a batch, semi-continuous or continuous manner.

However, considering the danger of hydrogen build-up if hydrogen is used as the active reducing component and the desire to avoid temperature variations over the photochromic article being processed, it is most simple to practice the process of the present invention by flowing the reducing atmosphere over the photochromic articles under a slight positive pressure in either a semicontinuous or continuous system.

In such systems the general rule is that excess reducing atmosphere is used to constantly flush the processing apparatus (avoiding the presence of undesired gases such as oxygen), avoid hot-spots on the surface of thephotochromic article at the article/reducing atmosphere interface and to insure that the desired reducing effect is obtained. To avoid highly turbulant conditions if a flowing semi-continuous or continuous or continuous system is being used, which might cause local hot spots on cold spots on the photochromic material, generally the pressure is maintained only slightly in excess of atmospheric to insure an even flow over the photochromic articles being processed.

The absolute amount of the reducing atmosphere used is obviously decided considering the total number of work pieces to be processed per unit time, and can easily be determined by one skilled in the art by a few trial process runs, e.g., in a flowing gas system generally one would select an appropriate temperature and time 7 of operation and then vary the flow rate of the reducing atmosphere until the desired tint is obtained. For example, in a muffle furnace with a diameter of 2 inches and a length of 8 inches a flow rate of 5 cc/second typically provides excellent results.

The temperature of the reduction process of the present invention is generally from about 300C. to about 600C.. This range is not limitative, and is set upon a balance of the following factors.

With respect to the minimum temperature, lower temperatures can be used. However, with decreasing temperatures longer times are required for the reduction process of the present invention and such is economically unpractical. At decreasingly lower temperatures, the thermal effects become lessened and the inherent photon activity of the photochromic material begins to predominate. As temperatures increasingly approach room temperature one does not obtain the permanent tinting effect of the present invention but,

rather, obtains only a semi-permanent effect which will soon disappear. Experimentation to date has not indicated any abrupt discontinuity in the reduction effect obtained in accordance with the present invention, rather, there is a gradual fall-off in the tinting effect as temperatures become lower than about 300C..

The maximum temperature is established primarily by the softening point of the photochromic article being processed. Generally, any excessive softening in the photochromic article will lead to a distortion of the shape thereof and, accordingly, a significant loss in commercial value. Since many photochromic glasses will tend to soften in the area of 600C., this is a practical working maximum for the process of the present invention. If one was altering the tint of a photochromic 6 float glass, of course, in such a case it would be permissible to operate at higher temperatures.

The general rule with plastic photochromic materials is that operation should be near the lower part of the above range since such materials typically show a ten dency to soften at rather low temperatures.

The time of the reduction process of the present invention is, of course, interdependent with the temperature of the reduction process of the present invention. If all other conditions are constant, the general rule is that at higher temperatures lesser processing times are required and at lower temperatures greater processing times are required. For many photochromic materials processing at about 300C. for about 15 minutes will provide excellent results while increasing the temperature to about 600C. will enable processing to be completed in about 4 to 5 minutes. For example, such times are most successfully used for materials as are disclosed in the Armistead et al., Stookey and like patents earlier incorporated by reference.

Increasing the temperature and/or time of processing increases the degree of tinting or color change effect obtained in accordance with the present invention, with decreasing temperatures and/or times lessening the degree of tinting or color change effect. Usually a few process runs are conducted with time the variable until the desired degree of tinting is obtained. If excessive times are necessary, the time can be decreased and temperature increased to obtain the desired tint. Obviously, both parameters can be simultaneously varied, if

desired.

Two caveats should be noted regarding the temperature and time of processing, however. If temperature and/or time is too low, a deeper tint than that of the starting photochromic material is achieved, of course, but the degree of tinting may be too slight to be easily visible to the naked eye. On the other hand, if temperature and/or time is too high, all of the photochromic element" in the photochromic material would be reduced, and one would be over tinting, thereby losing the photochromic effect. While in many instances there will be no objection to partially decreasing the photochromic effect, there would be no gain in destroying all photochromic activity. One should, of course, avoid reaction conditions which are so severe that oxides in photochromic glasses are reduced.

One general consideration with processing in accordance with the present invention relates to the thickness of the photochromic article being treated. The general rule is that the thicker the photochromic article the longer the time of processing and/or the higher the temperature of processing must be, generally time being the variable. The reason for this is that it appears, from results to date, that some type of diffusion effect is involved in the processof the present invention. The longer the time and/or the higher the temperature of processing, the deeper the reduction effect of the present invention penetrates into the photochromic material and the deeper the tint obtained.

Since a dark to light gradient of the tinting effect in accordance with the present invention is encountered from the surface of the photochromic article into the interior of the photochromic article, it will be appreciated that the present invention finds particular application with essentially finished photochromic articles, e.g., ground lenses, ready to install windows and the like. If one were to attempt to process an unfinished material or blank, generally the amount of grinding required to form a finished article would remove much of the deeper tints obtained in accordance with the present invention. Of course, this effect could be used to obtain photochromic articles ground on one side but not ground on the other side, the ground side illustrat- EXPOSURE TO ULTRAVIOLET RADIATION AT ELEVATED TEMPERATURES The first step of the process of the present invention can be used per se to effect a change in tint, as is described and claimed in applicants copending US. application Ser. No. 438,838 filed Feb. 1, 1974, entitled Process for Changing the Tint of a Photochromic Material and Material Formed Thereby."

However, with many materials it may be desirable to conduct the first processing step at low temperatures and/or times, whereby only a slight tinting is achieved, or in certain situations at high temperatures and/or times the tinting achieved in the first processing step may be insufficient for a particular purpose.

The second process step of the present invention deepens or darkens the tint achieved by the heating in a reducing atmosphere, and comprises subjecting the photochromic article from the first step of the process to ultraviolet irradiation before the article cools to beneath about 300C. The ultraviolet irradiation should be substantially completed before the article cools to beneath about 300C. as the effect of the irradiation decreases substantially at lower temperatures. Most preferably, irradiation is finished at a temperature above 300C.

For reasons which are not completely understood, the tint deepening effect of the second step of the present invention is not realized if, for example, the photochromic article from the first step is cooled and then reheated for ultraviolet irradiation.

In light of the parameters set out for the first processing step of the present invention, this will mean that one will generally initiate ultraviolet irradiation immediately upon completion of reduction processing. Some cooling is acceptable, of course, so long as the above parameters are observed. For instance, if heating was at 600C. the article might well cool to 525C. before ultraviolet irradiation is initiated.

In those instances where the photochromic article is reduction processed at a relatively high temperature,

ultraviolet irradiation is most simply carried out while the photochromic article is permitted to cool naturally in the air from substantially its temperature at the end of reduction processing to a temperature no less than about 300C. In this regard, the final temperature at the termination of ultraviolet irradiation is not overly important so long as it is not substantially below about 300C. For example, ultraviolet irradiation could be conducted from 600 to 450C., 550 to 475C, 400 to 300C., etc.

While ultraviolet irradiation can be conducted in a heated environment which slows the rate of cooling to permit longer irradiation times to be used, the photochromic article should not be elevated in temperature to any significance during ultraviolet irradiation as inferior results are obtained by temperature elevation once the natural cooling cycle of the photochromic article has begun.

In view of the danger of inferior results, the use of such an artificially heated environment should be avoided. and if used the minimum necessary heating should be used, e.g., on the order of C.

The ultraviolet irradiation most preferably has a wavelength of less than about 3600 A. Since generally air attenuation of ultraviolet irradiation below about 1800 A becomes appreciable, usually ultraviolet irradiation in the 1800 to 3600 A range will be used.

While irradiation of other wavelengths can be present, it does not benefit the process and in view of the ready commercial availability of ultraviolet sources generating within this range, e.g., a mercury arc lamp, little need exists to waste power on generating radiation of other wavelengths.

In order to achieve the increase in tinting from the ultraviolet irradiation the photochromic article should be subjected to an ultraviolet intensity at the surface thereof of 100 milliwatts/cm or greater. Results to date indicate that so long as this minimum intensity of exposure is met there is no substantial benefit to be gained by using greater intensities, in the sense of obtaining better product qualities, though at higher intensities the time of processing can be decreased somewhat.

Results to date indicate that with any practical ultraviolet source no harmful influence is exerted on the photochromic article, and there is no process limit of consequence on the maximum intensity of the irradiation.

However, considering that high intensity ultraviolet sources can pose a danger to the process operator and increase expense, generally no source will be used which provides an ultraviolet radiation intensity greatly in excess of about 100 watts/cm at practical operating distances.

Insofar as the time of irradiation is concerned, generally this will be established upon considering the degree of tinting from the first process step and the final degree of tinting desired. It must be kept in mind that the ultraviolet irradiation can also over tint the photochromic article since it is believed a further reduction of the active photochromic element" occurs during this step as is encountered with the first step of the process.

Generally the exact time of irradiation is empirically determined, i.e., at constant intensity the time of irradiation is increased until the desired tinting effect is obtained. Once the desired tint is achieved the irradiation is stopped, which halts the tinting effect.

For most photochromic articles processed in accordance with the preferred conditions for the first process step ultraviolet irradiation at an intensity of at least about 100 milliwatts/cm at the article surface for about 5 minutes provides an appreciable darkening in tint, with greater processing times continuing to deepen the tint. Under most conditions, ultraviolet irradiation is completed within about 10 minutes, though this value is not limitative.

Upon the cessation of ultraviolet irradiation the photochromic article can be removed and merely permitted to cool to room temperature for convenient handling.

The following specific examples illustrate preferred modes of practicing the present invention. These examples should not be taken as limitative on the present invention.

div

EXAMPLE 1 Armistead. et al. which had the following composition: 1

Component 7: by wt. (approx) SiO 55.) Al,(') 9.0 B [6.2 U0 2.65 NaO L85 PbO 5.05 BaO 6.7 ZrO 2.3 Ag 0.l7 Cl 0.29 Br 0.72 CuO 0.022 F 0.2 MG 0.022 CoO 0.012

For purposes ofthis example, two such lenses were placed on a stainless steel mesh support and inserted into a muffle furnace 4 inches in diameter and 12 inches in length. The muffle furnace was provided with a constant temperature zone at the center thereof maintained at a temperature of about 450C.

The muffle furnace had been purged with a 5% hydrogen/95% nitrogen (volume) flowing gas stream prior to the insertion of the lenses into the muffle furnace.

While maintaining the temperature of the center of the muffle furnace containing the lenses at 450C., the gaseous reducing atmosphere described above was flowed over the lenses for 8 minutes at a flow rate of 5 cc/second with a pressure slightly in excess of atmospheric.

After 8 minutes the lenses were removed from the muffle furnace and-immediately subjected to ultraviolet irradiation for 10 minutes while naturally cooling in the air.

The intensity of the ultraviolet irradiation was-about ll0 milliwatts/cm provided by a I000 watt mercury arc lamp (wavelength 3600 A) about 8 inches from the lenses.

The lenses, which had a yellow tint at the completion of the reducing gas treatment, were converted to a deeper yellow color, which was permanent and which did not interfere in any manner with the photochromic properties of the untreated glass lenses.

These glass lenses could be used with excellent results as shooters glasses.

EXAMPLE 2 ducing atmosphere for 12 minutes. The lenses which were a darkish yellow at the completion of the first process step illustrated a deep yellow-brownish tint after ultraviolet irradiation.

EXAMPLE 3 The procedure of Example 1 was duplicated except for maintaining the temperature in the center of the muffle furnace at 600C. and processing for 12 minutes as in Example 1. The lenses at the completion of processing exhibited a very dark brownish tint.

In all cases, the photochromic properties of the glasses were not degraded in any substantial manner 0 and yet the tinting effect of the present invention was achieved.

This result is illustrated by the attached figure which is a plot of percent transmittance against the wavelength of light irradiated on two identical glass samples as described in Example 1, one treated in accordance with the present invention (Curve B) and one not so treated (Curve A). While the treated glass illustrated a deep yellowish tone the untreated glass was substantially transparent. Reference to the FIGURE shows that the photochromic characteristics of both glasses were substantially identical.

While the invention has been particularly shown and described with reference to preferred embodiments thereof. it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

What is claimed is:

l. A process for permanently changing the tint of a photochromic inorganic bore silicate glass article containing submicroscopic particles of silver halide, without adverse effect on the photochromic properties thereof, which comprises heating the photochromic glass article at a temperature of at least about 300C to about 600C for from about 4 minutes to about 15 min-, utes in a gaseous reducing atmosphere having a free energy of formation greater than about 1 V2 to about 2 electron volts; and then prior to substantial cooling of said article subjecting said article while at an elevated temperature to ultraviolet irradiation, said heating in a gaseous reducing atmosphere imparting an initial tint to the photochromic article and said subjecting to ultraviolet irradiation being at a time and temperature sufficientto deepen said initial tint. 2. The process of claim 1, wherein the reducing atmosphere comprises hydrogen.

3. The process of claim 2, wherein the reducing atmosphere further comprises an inert carrier gas.

4. The process of claim 3, wherein the inert carrier gas is nitrogen.

5. The process of claim 1, wherein said article is subjected to ultraviolet irradiation prior to substantial cooling and while said elevated temperature is above about 300C.

6. The process of claim 5, wherein said elevated temperature is below about 600C.

7. The process of claim 6, wherein said ultraviolet irradiation is of an intensity of at least about milliwattslcm 8. The process of claim 5, wherein said article is subjected to ultraviolet irradiation while naturally cooling in air. 7

9. The process of claim 5, wherein said ultraviolet irradiation has a wavelength of less than about 3,600 A.

10. A photochromic article produced by the process of claim 1.

irradiation has a wavelength in the range of 1,800 to 14. The process of claim 12, wherein ultraviolet irradiation is completed within about 10 minutes.

15. The process of claim 13, wherein ultraviolet irradiation is completed within about 10 minutes. 

1. A PROCESS FOR PERMANENTLY CHANGING THE TINT OF A PHOTOCHROMIC INORGANIC BORE SILICATE GLASS ARTICLE CONTAINING SUBMICROSCOPIC PARTICLES OF SILVER HALIDE, WHITOUT ADVERSE EFFECT ON THE PHOTOCHROMIC PROPERTIES THEREOF, WHICH COMPRISES HEATING THE PHOTOCHROMIC GLASS ARTICLE AT A TEMPERATURE OF AT LEAST ABOUT 300*C TO ABOUT 600*C FOR FROM ABOUT 4 MINUTES TO ABOUT 15 MINUTES IN A GASEOUS REDUCING ATMOSPHERE HAVING A FREE ENERGY OF FORMATION GREATER THAN ABOUT 1 1/2 TO ABOUT 2 ELECTROON VOLTS; AND THEN PRIOR TO SUBSTANTIAL COOLING OF SAID ARTICLE SUBJECTING SAID ARTICLE WHILE AT AN ELEVATED-TEMPERATURE TO ULTRAVIOLET IRRADIATION. SAID HEATING IN A GASEOUS REDUCING ATMOSPHERE IMPARTING AN INITIAL TINT TO THE PHOTOCHROMIC ARTICLE AND SAI SUBJECTING TO ULTRAVIOLET IRRADIATION BEING AT A TIME AND TEMPERATURE SUFFICIENT TO DEEPEN SAID INITIAL TINT.
 2. The process of claim 1, wherein the reducing atmosphere comprises hydrogen.
 3. The process of claim 2, wherein the reducing atmosphere further comprises an inert carrier gas.
 4. The process of claim 3, wherein the inert carrier gas is nitrogen.
 5. The process of claim 1, wherein said article is subjected to ultraviolet irradiation prior to substantial cooling and while said elevated temperature is above about 300*C..
 6. The process of claim 5, wherein said elevated temperature is below about 600*C..
 7. The process of claim 6, wherein said ultraviolet irradiation is of an intensity of at least about 100 milliwatts/cm2.
 8. The process of claim 5, wherein said article is subjected to ultraviolet irradiation while naturally cooling in air.
 9. The process of claim 5, wherein said ultraviolet irradiation has a wavelength of less than about 3,600 A.
 10. A photochromic article produced by the process of claim
 1. 11. The process of claim 7, wherein said ultraviolet irradiation has a wavelength of less than about 3,600 A.
 12. The process of claim 5, wherein said ultraviolet irradiation has a wavelength in the range of 1,800 to 3,600 A.
 13. The process of claim 9, wherein said ultraviolet irradiation has a wavelength in the range of 1,800 to 3,600 A.
 14. The process of claim 12, wherein ultraviolet irradiation is completed within about 10 minutes.
 15. The process of claim 13, wherein ultraviolet irradiation is completed within about 10 minutes. 